Electron transfer rate modulation with mid-IR in butadiyne-bridged donor-bridge-acceptor compounds.

Controlling electron transfer (ET) processes in donor-bridge-acceptor (DBA) compounds by mid-IR excitation can enhance our understanding of the ET dynamics and may find practical applications in molecular sensing and molecular-scale electronics. Alkyne moieties are attractive to serve as ET bridges, as they offer the possibility of fast ET and present convenient vibrational modes to perturb the ET dynamics. Yet, these bridges introduce complexity because of the strong torsion angle dependence of the ET rates and transition dipoles among electronic states and a shallow torsion barrier. In this study, we implemented ultrafast 3-pulse laser spectroscopy to investigate how the ET from the dimethyl aniline (D) electron donor to the N-isopropyl-1,8-napthalimide (NAP) electron acceptor can be altered by exciting the CC stretching mode (νCC) of the butadiyne bridge linking the donor and acceptor. The electron transfer was initiated by electronically exciting the acceptor moiety at 400 nm, followed by vibrational excitation of the alkyne, νCC, and detecting the changes in the absorption spectrum in the visible spectral region. The experiments were performed at different delay times t1 and t2, which are the delays between UV-mid-IR and mid-IR-Vis pulses, respectively. Two sets of torsion-angle conformers were identified, one featuring a very fast mean ET time of 0.63 ps (group A) and another featuring a slower mean ET time of 4.3 ps (group B), in the absence of the mid-IR excitation. TD-DFT calculations were performed to determine key torsion angle dependent molecular parameters, including the electronic and vibrational transition dipoles, transition frequencies, and electronic couplings. To describe the 3-pulse data, we developed a kinetic model that includes a locally excited, acceptor-based S2 state, a charge separated S1 state, and their vibrationally excited counterparts, with either excited νCC (denoted as S1Atr, S1Btr, S2Atr, and S2Btr, where tr stands for the excited triplet bond, νCC) or excited daughter modes of the νCC relaxation (S1Ah, S1Bh, S2Ah, and S2Bh, where h stands for vibrationally hot species). The kinetic model was solved analytically, and the species-associated spectra (SAS) were determined numerically using a matrix approach, treating first the experiments with longer t1 delays and then using the already determined SAS for modeling the experiments with shorter t1 delays. Strong vibronic coupling of νCC and of vibrationally hot states makes the analysis complicated. Nevertheless, the SAS were identified and the ET rates of the vibrationally excited species, S2Atr, S2Btr and S2Bh, were determined. The results show that the ET rate for the S2A species is ca. 1.2-fold slower when the νCC mode is excited. The ET rate for species S2B is slower by ca. 1.3-fold if the compound is vibrationally hot and is essentially unchanged when the νCC mode is excited. The SAS determined for the tr and h species resemble the SAS for their respective precursor species in the 2-pulse transient absorption experiments, which validates the procedure used and the results.

Probing the Hydrophobic Region of a Lipid Bilayer at Specific Depths Using Vibrational Spectroscopy.

A novel spectroscopic approach for studying the flexibility and mobility in the hydrophobic interior of lipid bilayers at specific depths is proposed. A set of test compounds featuring an azido moiety and a cyano or carboxylic acid moiety, connected by an alkyl chain of different lengths, was synthesized. FTIR data and molecular dynamics calculations indicated that the test compounds in a bilayer are oriented so that the cyano or carboxylic acid moiety is located in the lipid head-group region, while the azido group stays inside the bilayer at the depth determined by its alkyl chain length. We found that the asymmetric stretching mode of the azido group (νN3) can serve as a reporter of the membrane interior dynamics. FTIR and two-dimensional infrared (2DIR) studies were performed at different temperatures, ranging from 22 to 45 °C, covering the Lß-Lα phase transition temperature of dipalmitoylphosphatidylcholine (∼41 °C). The width of the νN3 peak was found to be very sensitive to the phase transition and to the temperature in general. We introduced an order parameter, SN3, which characterizes restrictions to motion inside the bilayer. 2DIR spectra of νN3 showed different extents of inhomogeneity at different depths in the bilayer, with the smallest inhomogeneity in the middle of the leaflet. The spectral diffusion dynamics of the N3 peak was found to be dependent on the depth of the N3 group location in the bilayer. The obtained results enhance our understanding of the bilayer dynamics and can be extended to investigate membranes with more complex compositions.

Hydrogen-Bonded Complexes in Binary Mixture of Imidazolium-Based Ionic Liquids with Organic Solvents.

Though local structures in ionic liquids are dominated by strong Coulomb forces, directional hydrogen bonds can also influence the physicochemical properties of imidazolium-based ionic liquids. In particular, the C-2 position of the imidazolium cation is acidic and can bind with suitable hydrogen bond acceptor sites of molecular solvents dissolved in imidazolium-based ionic liquids. In this report, we identify hydrogen-bonded microenvironments of the model ionic liquid, 1-ethyl-3-methylimidazolium tris(pentafluoroethyl) trifluorophosphate, and the changes that occur when molecular solvents are dissolved in it by using a C-D infrared reporter at the C-2 position of the cation. Our linear and nonlinear infrared experiments, along with computational studies, indicate that the molecular solvent dimethyl sulfoxide can form strong hydrogen-bonded dimers with the cation of the ionic liquid at the C-2 position. In contrast, acetone, which is also a hydrogen bond acceptor similar to dimethyl sulfoxide, does not show evidence of cation-solvent hydrogen-bonded conformers at the C-2 position. The outcome of our study on a broad scale strengthens the importance of cation-solute interactions in ionic liquids.

Maximum propagation speed and Cherenkov effect in optical phonon transport through periodic molecular chains.

Optical phonons serve as the fast and efficient carriers of energy across periodic polymers due to their delocalization, large group velocity because of covalent bonding, and large energy quantum compared to that for acoustic phonons as it was observed in a number of recent measurements in different oligomers. However, this transport is dramatically sensitive to anharmonic interactions, including the unavoidable interaction with acoustic phonons responsible for transport decoherence, suppressing ballistic transport at long distances. Here, we show that this decoherence is substantially suppressed if the group velocity of optical phonons is less than the sound velocity of acoustic phonons; otherwise, ballistic transport is substantially suppressed by a Cherenkov-like emission of acoustic phonons. This conclusion is justified considering energy and momentum conservation during phonon absorption or emission and supported by the numerical evaluation of the lifetimes of the optical phonons. It is also consistent with the recent experimental investigations of ballistic optical phonon transport in oligomers with the minor exception of relatively short oligophenylenes.

Tracking Energy Transfer across a Platinum Center.

Rigid, conjugated alkyne bridges serve as important components in various transition-metal complexes used for energy conversion, charge separation, sensing, and molecular electronics. Alkyne stretching modes have potential for modulating charge separation in donor-bridge-acceptor compounds. Understanding the rules of energy relaxation and energy transfer across the metal center in such compounds can help optimize their electron transfer switching properties. We used relaxation-assisted two-dimensional infrared spectroscopy to track energy transfer across metal centers in platinum complexes featuring a triazole-terminated alkyne ligand of two or six carbons, a perfluorophenyl ligand, and two tri(p-tolyl)phosphine ligands. Comprehensive analyses of waiting-time dynamics for numerous cross and diagonal peaks were performed, focusing on coherent oscillation, energy transfer, and cooling parameters. These observables augmented with density functional theory computations of vibrational frequencies and anharmonic force constants enabled identification of different functional groups of the compounds. Computations of vibrational relaxation pathways and mode couplings were performed, and two regimes of intramolecular energy redistribution are described. One involves energy transfer between ligands via high-frequency modes; the transfer is efficient only if the modes involved are delocalized over both ligands. The energy transport pathways between the ligands are identified. Another regime involves redistribution via low-frequency delocalized modes, which does not lead to interligand energy transport.

Competition of Several Energy-Transport Initiation Mechanisms Defines the Ballistic Transport Speed.

The ballistic regime of vibrational energy transport in oligomeric molecular chains occurs with a constant, often high, transport speed and high efficiency. Such a transport regime can be initiated by exciting a chain end group with a mid-infrared (IR) photon. To better understand the wavepacket formation process, two chemically identical end groups, azido groups with normal, 14N3-, and isotopically substituted, 15N3-, nitrogen atoms, were tested for wavepacket initiation in compounds with alkyl chains of n = 5, 10, and 15 methylene units terminated with a carboxylic acid (-a) group, denoted as 14N3Cn-a and 15N3Cn-a. The transport was initiated by exciting the azido moiety stretching mode, the νN≡N tag, at 2100 cm-1 (14N3Cn-a) or 2031 cm-1 (15N3Cn-a). Opposite to the expectation, the ballistic transport speed was found to decrease upon 14N3 → 15N3 isotope editing. Three mechanisms of the transport initiation of a vibrational wavepacket are described and analyzed. The first mechanism involves the direct formation of a wavepacket via excitation with IR photons of several strong Fermi resonances of the tag mode with the νN═N + νN-C combination state while each of the combination state components is mixed with delocalized chain states. The second mechanism relies on the vibrational relaxation of an end-group-localized tag into a mostly localized end-group state that is strongly coupled to multiple delocalized states of a chain band. Harmonic mixing of νN═N of the azido group with CH2 wagging states of the chain permits a wavepacket formation within a portion of the wagging band, suggesting a fast transport speed. The third mechanism involves the vibrational relaxation of an end-group-localized mode into chain states. Two such pathways were found for the νN≡N initiation: The νN═N mode relaxes efficiently into the twisting band states and low-frequency acoustic modes, and the νN-C mode relaxes into the rocking band states and low-frequency acoustic modes. The contributions of the three initiation mechanisms in the ballistic energy transport initiated by νN≡N tag are quantitatively evaluated and related to the experiment. We conclude that the third mechanism dominates the transport in alkane chains of 5-15 methylene units initiated with the νN≡N tag and the wavepacket generated predominantly at the CH2 twisting band. The isotope effect of the transport speed is attributed to a larger contribution of the faster wavepackets for 14N3Cn-a or to the different breadth of the wavepacket within the twisting band. The study offers a systematic description of different transport initiation mechanisms and discusses the requirements and features of each mechanism. Such analysis will be useful for designing novel materials for energy management.

Unidirectional coherent energy transport via conjugated oligo(p-phenylene) chains.

We discovered a way to funnel high-frequency vibrational quanta rapidly and unidirectionally over large distances using oligo(p-phenylene) chains. After mid-IR photon photoexcitation of a -COOH end group, the excess energy is injected efficiently into the chain, forming vibrational wavepackets that propagate freely along the chain. The transport delivers high-energy vibrational quanta with a range of transport speeds reaching 8.6 km/s, which exceeds the speed of sound in common metals (∼5 km/s) and polymers (∼2 km/s). Efficiencies of energy injection into the chain and transport along the chain are found to be very high and dependent on the extent of conjugation across the structure. By tuning the degree of conjugation via electronic doping of the chain, the transport speed and efficiency can be controlled. The study opens avenues for developing materials with controllable energy transport properties for heat management, schemes with efficient energy delivery to hard-to-reach regions, including transport against thermal gradients, and ways for initiating chemical reactions remotely.

Surface-enhanced ultrafast two-dimensional vibrational spectroscopy with engineered plasmonic nano-antennas.

Development of noble metal nanostructure substrates that provide strong near-field enhancements enables applications of linear and nonlinear infrared (IR) spectroscopies to study minute sample quantities, such as nanometer thick films and molecular monolayers. Large near-field enhancements of the electric fields used for spectroscopic interrogation of molecules at the nanostructure surface result in enhancement of the spectroscopic signatures. This enhancement scales with the nonlinear order of the method, providing particularly large signal gains for third- and fifth-order IR methods, reaching 106 and 108 raw enhancement factors, not adjusted to the amount of interrogated sample. In this perspective, we overview the advances in the development of nano-arrays of antenna-like nanostructures for mid-IR measurements and illustrate their use in linear and especially nonlinear two-dimensional IR approaches. We discuss how studies of the interaction mechanisms between light, plasmonic antennas, and molecular excitations benefit from the nonlinear two-dimensional time-resolved methods, which involve high-order scaling of the signal with the excitation field, high sensitivity to signal localization, and coherence of the excitation over a broad bandwidth. On the other hand, we demonstrate how studies of molecular structure and ultrafast dynamics by these advanced spectroscopic methods benefit from surface enhancement of signals by plasmonic antennas.

Proving and Probing the Presence of the Elusive C-H⋠⋠⋠O Hydrogen Bond in Liquid Solutions at Room Temperature.

Hydrogen bonds (H bonds) play a major role in defining the structure and properties of many substances, as well as phenomena and processes. Traditional H bonds are ubiquitous in nature, yet the demonstration of weak H bonds that occur between a highly polarized C-H group and an electron-rich oxygen atom, has proven elusive. Detailed here are linear and nonlinear IR spectroscopy experiments that reveal the presence of H bonds between the chloroform C-H group and an amide carbonyl oxygen atom in solution at room temperature. Evidence is provided for an amide solvation shell featuring two clearly distinguishable chloroform arrangements that undergo chemical exchange with a time scale of about 2 ps. Furthermore, the enthalpy of breaking the hydrogen bond is found to be 6-20 kJ mol-1 . Ab-initio computations support the findings of two distinct solvation shells formed by three chloroform molecules, where one thermally undergoes hydrogen-bond making and breaking.

Low-Temperature Vibrational Energy Transport via PEG Chains.

We used relaxation-assisted two-dimensional infrared spectroscopy to study the temperature dependence (10-295 K) of end-to-end energy transport across end-decorated PEG oligomers of various chain lengths. The excess energy was introduced by exciting the azido end-group stretching mode at 2100 cm-1 (tag); the transport was recorded by observing the asymmetric C═O stretching mode of the succinimide ester end group at 1740 cm-1. The overall transport involves diffusive steps at the end groups and a ballistic step through the PEG chain. We found that at lower temperatures the through-chain energy transport became faster, while the end-group diffusive transport time and the tag lifetime increase. The modeling of the transport using a quantum Liouville equation linked the observations to the reduction of decoherence rate and an increase of the mean-free-path for the vibrational wavepacket. The energy transport at the end groups slowed down at low temperatures due to the decreased number and efficiency of the anharmonic energy redistribution pathways.

Symmetry controlled photo-selection and charge separation in butadiyne-bridged donor-bridge-acceptor compounds.

Electron transfer (ET) in donor-bridge-acceptor (DBA) compounds depends strongly on the structural and electronic properties of the bridge. Among the bridges that support donor-acceptor conjugation, alkyne bridges have attractive and unique properties: they are compact, possess linear structure permitting access to high symmetry DBA molecules, and allow torsional motion of D and A, especially for longer bridges. We report conformation dependent electron transfer dynamics in a set of novel DBA compounds featuring butadiyne (C4) bridge, N-isopropyl-1,8-napthalimide (NAP) acceptors, and donors that span a range of reduction potentials (trimethyl silane (Si-C4-NAP), phenyl (Ph-C4-NAP), and dimethyl aniline (D-C4-NAP)). Transient mid-IR absorption spectra of the C[triple bond, length as m-dash]C bridge stretching modes, transient spectra in the visible range, and TD-DFT calculations were used to decipher the ET mechanisms. We found that the electronic excited state energies and, especially, the transition dipoles (S0 → Sn) depend strongly on the dihedral angle (θ) between D and A and the frontier orbital symmetry, offering an opportunity to photo-select particular excited states with specific ranges of dihedral angles by exciting at chosen wavelengths. For example, excitation of D-C4-NAP at 400 nm predominantly prepares an S1 excited state in the planar conformations (θ ∼ 0) but selects an S2 state with θ ∼ 90°, indicating the dominant role of the molecular symmetry in the photophysics. Moreover, the symmetry of the frontier orbitals of such DBA compounds not only defines the photo-selection outcome, but also determines the rate of the S2 → S1 charge separation reaction. Unprecedented variation of the S2-S1 electronic coupling with θ by over four orders of magnitude results in slow ET at θ ca. 0° and 90° but extremely fast ET at θ of 20-60°. The unique features of high-symmetry alkyne bridged DBA structures enable frequency dependent ET rate selection and make this family of compounds promising targets for the vibrational excitation control of ET kinetics.

Orientational Dependence of Cofacial Porphyrin-Quinone Electronic Interactions within the Strong Coupling Regime.

We examine the relative magnitudes of electronic coupling HDA in two face-to-face rigid and diastereomeric (porphinato)zinc(II)-quinone (PZn-Q) assemblies, 1ß-ZnA and 1ß-ZnB, in which the six quinonyl carbon atoms lie in virtually identical arrangements relative to the PZn plane at sub-van der Waals donor-acceptor (D-A) interplanar separations. Steady-state and time-resolved transient optical data and computational studies show that minor differences in relative D-A cofacial orientation give rise to disparate HDA magnitudes for both photoinduced charge separation (CS) and thermal charge recombination (CR). Time-dependent density functional theory (TDDFT) computations illuminate the nature of direct charge transfer states and the electronic structural factors that give rise to these differential HDAs. These data show more extensive mixing of locally excited (LE) and CS states in 1ß-ZnA relative to 1ß-ZnB and that these HDA differences track the magnitudes of electronic coupling matrix elements determined from steady-state electronic spectral data and thermal CR rate constants measured via pump-probe spectroscopy. Collectively, this work shows that electron transfer dynamics may be manipulated in cofacial D-A systems, even at sub-van der Waals contact, provided that conformational rigidity precludes structural fluctuations that modulate D-A interactions on the charge transfer time scale.

Unsymmetrical Bis-Alkynyl Complexes Based on Co(III)(cyclam): Synthesis, Ultrafast Charge Separation, and Analysis.

Donor-bridge-acceptor (D-B-A) systems with a polarizable bridge can afford rapid photoinduced electron transfer dynamics that may be susceptible to rate modulation by infrared excitation. We describe the synthesis, characterization, and electronic structure of a class of readily assembled D-B-A structures linked by a cobalt cyclam bridge. The reaction between [Co(cyclam)Cl2]Cl and 4-ethynyl-N-isopropyl-1,8-naphthalimide (HC2NAPiPr) yields [Co(cyclam)(C2NAPiPr)Cl]Cl (1), which reacts with LiC2Y at -78 °C to afford [Co(cyclam)(C2NAPiPr)(C2D)]Cl with D as C6H4-4-NMe2 (2a), NAPiPr (2b), Ph (2c), and C6H4-4-N(4-MeOPh)2 (2d). Molecular structures of 1 and 2a were established using single-crystal X-ray diffraction, while the redox properties and fluorescence profiles of compounds 1 and 2 were examined using voltammetric and steady-state emission techniques, respectively. The electronic structures and photophysical properties of these compounds were studied using density functional theory and time-dependent density functional theory methods. The excited-state dynamics of compounds 1, 2a, and 2d were explored using femtosecond transient absorption spectroscopy with 400 nm excitation and detection in both the visible and mid-IR spectral regions. Formation of a long-lived excited state was complete within 20 ps of excitation in all three compounds. Ultrafast spectral changes observed in 2a and 2d within the first 20 ps indicated the formation of a charge separated state (CS state, D+-B-A-) with characteristic times of less than 0.1 and 0.25 ps, respectively. The CS state undergoes rapid charge recombination (8 ps in 2a and 4 ps in 2d). The CS dynamics is facilitated by the Co center, which mixes the bright NAP-centered electronic state with a pure CS state. The mixing strength depends on the donor energetics and conformation, which significantly influences the charge transfer dynamics in 2a and 2d.

Intense-field interaction regime with weak laser pulses and localized plasmonic enhancement: Reference-free demonstration by 3rd- and 5th-order infrared spectroscopies.

In bulk materials, intense field interaction is accompanied by undesired nonresonant processes. Plasmonic nanostructures localize enhanced fields exclusively in their vicinity. We report a 4-fold vibrational population inversion between all the excited and the ground states in the molecular monolayer on the surface of gold nanoantennas. Excited population assessment relies on a novel reference-sample-free evaluation of the field enhancement with 5th- and 3rd-order nonlinear infrared spectroscopies and on quantitative modeling of coherent excitation dynamics. This study opens opportunities for precise population control utilizing population inversion for vibrational transitions using weak fields.

Ballistic and diffusive vibrational energy transport in molecules.

Energy transport in molecules is essential for many areas of science and technology. Strong covalent bonds of a molecular backbone can facilitate the involvement of the molecule's high-frequency modes in energy transport, which, under certain conditions, makes the transport fast and efficient. We discuss such conditions and describe various transport regimes in molecules, including ballistic, diffusive, directed diffusion, and intermediate regime cases, in light of recently developed experimental and theoretical approaches.

How can infra-red excitation both accelerate and slow charge transfer in the same molecule?

A UV-IR-Vis 3-pulse study of infra-red induced changes to electron transfer (ET) rates in a donor-bridge-acceptor species finds that charge-separation rates are slowed, while charge-recombination rates are accelerated as a result of IR excitation during the reaction. We explore the underpinning mechanisms for this behavior, studying IR-induced changes to the donor-acceptor coupling, to the validity of the Condon approximation, and to the reaction coordinate distribution. We find that the dominant IR-induced rate effects in the species studied arise from changes to the density of states in the Marcus curve crossing region. That is, IR perturbation changes the probability of accessing the activated complex for the ET reactions. IR excitation diminishes the population of the activated complex for forward (activationless) ET, thus slowing the rate. However, IR excitation increases the population of the activated complex for (highly activated) charge recombination ET, thus accelerating the charge recombination rate.

Radiative Enhancement of Linear and Third-Order Vibrational Excitations by an Array of Infrared Plasmonic Antennas.

Infrared gold antennas localize enhanced near fields close to the metal surface, when excited at the frequency of their plasmon resonance, and amplify vibrational signals from the nearby molecules. We study the dependence of the signal enhancement on the thickness of a polymer film containing vibrational chromophores, deposited on the antenna array, using linear (FTIR) and third-order femtosecond vibrational spectroscopy (transient absorption and 2DIR). Our results show that for a film thickness beyond only a few nanometers the near-field interaction is not sufficient to account for the magnitude of the observed signal, which nevertheless has a clear Fano line shape, suggesting a radiative origin of the molecule-plasmon interaction. The mutual radiative damping of plasmonic and molecular transitions leads to the spectroscopic signal of a molecular vibrational excitation to be enhanced by up to a factor of 50 in the case of linear spectroscopy and over 2000 in the case of third-order spectroscopy. A qualitative explanation for the observed effect is given by the extended coupled oscillators model, which takes into account both near-field and radiative interactions between the plasmonic and molecular transitions.

Expanding the Scope of Ligand Substitution from [M(S2C2Ph2] (M = Ni2+, Pd2+, Pt2+) To Afford New Heteroleptic Dithiolene Complexes.

The scope of direct substitution of the dithiolene ligand from [M(S2C2Ph2)2] [M = Ni2+ (1), Pd2+ (2), Pt2+ (3)] to produce heteroleptic species [M(S2C2Ph2)2Ln] (n = 1, 2) has been broadened to include isonitriles and dithiooxamides in addition to phosphines and diimines. Collective observations regarding ligands that cleanly produce [M(S2C2Ph2)Ln], do not react at all, or lead to ill-defined decomposition identify soft σ donors as the ligand type capable of dithiolene substitution. Substitution of MeNC from [Ni(S2C2Ph2)(CNMe)2] by L provides access to a variety of heteroleptic dithiolene complexes not accessible from 1. Substitution of a dithiolene ligand from 1 involves net redox disproportionation of the ligands from radical monoanions, -S•SC2Ph2, to enedithiolate and dithione, the latter of which is an enhanced leaving group that is subject to further irreversible reactions.

Two-Dimensional Fano Lineshapes in Ultrafast Vibrational Spectroscopy of Thin Molecular Layers on Plasmonic Arrays.

Two-dimensional femtosecond infrared (2DIR) spectroscopy routinely provides insights into molecular structure and ultrafast dynamics in 1-100 µm thick bulk samples. Confinement of molecules to surfaces, gaps, crevices, and other topographic features, frequently encountered on the nanometer length scale, significantly alters their structure and dynamics, affecting physical and chemical properties. Amplification of 2DIR signals by the plasmon-enhanced fields around metal nanostructures can permit structural and dynamics measurements of the confined molecules. Fano resonances, induced by the interaction between laser pulses, plasmon, and vibrational modes significantly distort 2D lineshapes. For different detuning from plasmon resonance, the interference between multiple signal components leads to different line shape asymmetry, which we demonstrate on a set of linear absorption, transient absorption, and 2DIR spectra. An intuitive model used to describe experimental data points to the interference's origin. Our results will facilitate the application of surface-enhanced 2DIR spectroscopy for studies of molecular structure and dynamics in a nanoconfined environment.